Intumescent nanostructured materials and methods of manufacturing same

ABSTRACT

An intumescent nanostructured material for thermal protection comprising a member including a plurality of nanostructured materials, and an intumescent material associated with the member and configured to react in the presence of a heat source to form a foam for thermally insulating the member from the heat source. The member may be a non-woven sheet, a woven sheet, a yarn, or a network, and may be configured to conduct thermal energy away from a heat source. A solution comprising a plurality of nanostructured materials, an intumescent material, and a solvent, wherein the solution has a viscosity suitable for coating or spraying onto a surface of a substrate. The solution may have a viscosity of about 3000 centipoise to about 6000 centipoise, and possibly less than about 1000 centipoise. The solution, when dried on the substrate, may form a thermally-protective coating on the substrate.

BACKGROUND

The general field of fire protection of both structures and peopledepends on materials that can insulate as well as spread and dissipateheat. In particular, the field of intumescent materials relies onchemical reactions that absorb heat, create gasses and drive phasechanges to create foams that help insulate. Present applications arelimited as it can be difficult to accommodate intumescent materials intoor on other materials, and to control properties of the foam createdduring a thermal event. Further, intumescent foams can break downquickly in the presence of a heat source, thereby limiting a durationfor which they can protect structures and people from harm. Stillfurther, intumescent foams have limited capabilities for dissipatingheat away from a heat source.

SUMMARY

The present disclosure is directed to an intumescent nanostructuredmaterial for thermal protection. The thermal protection material maycomprise a member, such as a non-woven sheet, a woven sheet, a yarn, ora pulp-like network, made of or otherwise containing a plurality ofnanostructured materials, as well as an intumescent material associatedwith the member. The member, in some aspects, may be configured to actas scaffolding for accommodating and holding the intumescent material inplace, as well as for conducting heat energy away from a heat source toavoid degradation or damage resulting from localized hot spots. Theintumescent material, in some aspects, may be configured to react in thepresence of the heat source to form a foam for thermally insulating themember (and any underlying structure to be protected) from the heatsource.

Unique synergies between the nanostructured materials and theintumescent material provide highly-effective thermal and fireprotection greater than that offered simply by its parts. The pluralityof nanostructures forming the member may, on the nano-scale, promotefoam morphologies having superior insulating and structural properties.Further, the member and the intumescent material may act to protect oneanother from heat, thereby improving the overall effectiveness andlongevity of the thermal protection material.

The plurality of nanostructured materials, in some embodiments, may becoated with a ceramifying polymer material and/or a flame retardant forprotecting the nanostructured materials from oxidation in the presenceof the heat source. Further, the intumescent material may be combinedwith a blowing agent that thermally decomposes to produce gasses thatfacilitate formation of the foam.

Various embodiments of the non-woven sheet member may have a pluralityof layers of intermingled and compacted nanotubes. Some of the nanotubesbetween adjacent layers may be intermingled with one another such thatan adequate number of contact sites exists to bond the adjacent layerstogether to form a cohesive sheet having a layered structure similar tophyllo-dough. Such a non-woven sheet member may be configured to providein-plane thermal conductivity for dissipating heat laterally away from aheat source, while minimizing through-plane thermal conductivity. In anembodiment, the non-woven member may have a nanotube areal density ofabout 20 g/m² to about 30 g/m².

Various embodiments of the yarn member may be defined by plurality ofintermingled and twisted carbon nanotubes. The yarn member may beconfigured to provide thermal conductivity along its length, and toprovide scaffolding structure for promoting formation of a layer ofthermally-insulating foam as the intumescent material reacts in thepresence of heat. In an embodiment, the yarn member may have a nanotubelinear density of about 1 Tex to about 100 Tex.

Various embodiments of the woven member may be defined by a plurality ofnanostructured yarn s woven, braided, or knitted with one another. Thewoven member may be configured to provide in-plane thermal conductivityalong pathways defined by the plurality of nanostructured yarns.

Various embodiments of the pulp-like network may be formed by coating orspraying a solution of nanostructured materials, intumescent material,and solvent onto a substrate. The solution, in some embodiments, mayhave a viscosity of about 3000 centipoise to about 6000 centipoise, andin some cases, less than about 1000 centipoise. The nanostructuredmaterials may form into a network on the substrate as the solutiondries, providing scaffolding for accommodating and holding theintumescent material, as well as providing conduction pathways along thesurface of the substrate for dissipating heat away from hot spots.

DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1C depicts schematic views of a intumescent nanostructuredmaterial for thermal protection, including a non-woven member, a yarnmember, and a non-woven member, respectively, according to variousembodiments of the present disclosure;

FIG. 2 depicts a intumescent nanostructured material coated onto a wirefor thermal protection, according to an embodiment of the presentdisclosure;

FIG. 3 depicts a non-woven nanotube sheet, according to an embodiment ofthe present disclosure;

FIG. 4 depicts a cross-sectional view of a phyllo-dough arrangement ofnanotube layers within a non-woven nanotube sheet, according to anembodiment of the present disclosure;

FIG. 5 depicts a system for forming a carbon nanotube sheet according toan embodiment of the present disclosure;

FIGS. 6A and 6B depict a system for harvesting a carbon nanotube sheetaccording to an embodiment of the present disclosure; and

FIGS. 7-9 depict various systems for forming a nanotube yarn accordingto various embodiments of the present disclosure.

TECHNICAL FIELD

The present invention relates to flame resistant materials, and moreparticularly, heat and flame resistant articles manufactured fromnanotubes and intumescent materials.

DESCRIPTION OF SPECIFIC EMBODIMENTS

Embodiments of the present disclosure provide an intumescentnanostructured material 100 having properties well-suited for thermalprotection and/or fire protection. Various embodiments of intumescentnanostructured material 100 may be provided as defined members, such assheets or yarns, for use as or incorporation into articles such astextiles, while others may come in the form of a viscous solution thatcan be coated or sprayed onto structures requiring protection from heatand/or flame and dried to form thermally-protective coatings. Uniquesynergies between the carbon nanotubes and intumescents of thepresently-disclosed material 100 provide highly-effective thermal andfire protection greater than that offered simply by its parts, asdescribed in more detail herein.

Referring to FIGS. 1 and 2, embodiments of intumescent nanostructuredmaterial 100 may generally include a CNT member 200, such woven nanotubesheets, non-woven nanotube sheets, nanotube yarns, and nanotubenetworks, as well as an intumescent material 300. Generally speaking,intumescent materials are materials that release gasses upon heating,either through a chemical reaction or phase change. In variousembodiments, CNT member 200 be coated or impregnated with intumescentmaterial 300 and/or be formed from nanotubes pre-coated with intumescentmaterial 300. CNT member 200, owing to the thermal conductivity of itsnanotubes, as well as thermally conductive pathways created by theparticular arrangement of nanotubes throughout the plane of member 200,may act to dissipate heat away from a heat source near material 100thereby offering thermal protection. Intumescent material 300 may offerthermal protection by undergoing an endothermic chemical reaction and/orphase change in response to the application of heat to material 100 thatremoves the energy of vaporization while forming a foam that furtherinsulates material 100 from the heat source.

While each component of intumescent nanostructured material 100 mayserve a particular purpose in its own individual capacity, synergiesbetween components of nanostructured material 100 provide for enhancedthermal protection characteristics beyond the sum of the individualparts of material 100. As further described in more detail below, CNTmember 200, in one aspect, may serve as scaffolding for accommodatingintumescent material 300 into various articles that may not otherwiseaccommodate intumescents in a suitable fashion, and holding intumescentmaterial 300 in place on or within the article. In another aspect, CNTmember 200 may provide, on the nano-scale, scaffolding for not onlysupporting the formation of insulating foams, but also influencing theirspecific morphologies, as intumescent material 300 reacts with anapplied heat source. In doing so, the resulting open- and/or closed-cellfoams generated from intumescent material 300 may have superiorinsulating properties when compared with those foams formed from similarintumescent materials 300 on or in other substrates or structures. Stillfurther, CNT member 200 and intumescent material 300 act to protect oneanother from the applied heat, thereby improving the overalleffectiveness and longevity of material 100 in providing thermalprotection. In particular, by dissipating heat away from a hot spot, CNTmember 200 may reduce the amount of heat to which intumescent material300 is exposed, thereby delaying or slowing the reaction of intumescentmaterial 300. This allows intumescent material 300 to vaporize at aslower rate, thereby removing the energy of vaporization over a longerperiod of time and improving the longevity of the foam by delaying itsformation. Intumescent material 300, in turn, may protect CNT member 200by itself dissipating heat energy and insulating CNT member 200 fromheat exposure and its degrading effects on its structural integrity andthat of its individual nanotubes. Stated otherwise, each protects theother, allowing material 100 to provide better overall thermalprotection for longer periods of time.

Some embodiments of intumescent nanostructured material 100 may furtherinclude additives such as flame retardants and ceramifying polymers 400such as polysilazane, polyureasilazane (PSZ) and other poly silazanes,such as Polyureamethylvinylsilazane Ceraset®, to enhance the strength ofthe CNT member 200 and its oxidation resistance characteristics, asfurther provided in more detail below.

CNT Member 200

Presently, there exist multiple processes and variations thereof forgrowing nanotubes, and forming yarns, sheets or cable structures madefrom these nanotubes. These include: (1) Chemical Vapor Deposition(CVD), a common process that can occur at near ambient or at highpressures, and at temperatures above about 400° C., (2) Arc Discharge, ahigh temperature process that can give rise to tubes having a highdegree of perfection, and (3) Laser ablation.

The present invention, in one embodiment, employs a CVD process orsimilar gas phase pyrolysis procedures known in the industry to generatethe appropriate nanostructures, including carbon nanotubes. Growthtemperatures for a CVD process can be comparatively low ranging, forinstance, from about 400° C. to about 1350° C. Carbon nanotubes (CNTs),may be characterized as single wall (SWNT), few wall (FWNT) or multiwall(MWNT). In this disclosure SWNT are described as consisting of a singlegraphene layer, FWNT will exhibit 2 or 3 layers in the wall structure,and MWNT walls will consist of 4 or more graphene layers. Although SWNT,FWNT and MWNT may be grown, in certain instances, FWNT may be preferreddue to their higher growth rate relative to SWNT, and better propertiesthan MWNT. Carbon Nanotubes may be grown, in an embodiment of thepresent invention, by exposing nanoscaled catalyst particles (forexample 1 to 30 nanometers in diameter) in the presence of reagentcarbon-containing gases (i.e., gaseous carbon source). In particular,the nanoscaled catalyst particles may be introduced into the reagentcarbon-containing gases, either by addition of existing particles or byin situ synthesis of the particles from a metal-organic precursor, oreven non-metallic catalysts. The formation and growth by CVD of carbonnanotubes in the gas phase, unbound by a substrate, is generallyreferred to as Floating Catalyst CVD (FC-CVD). The enhanced propertiesof FC-CVD are believed to be due to their tendency to form an extendednetwork of branched nanotube bundles and aggregates as they cool fromthe furnace growth-zone. The network of branched nanotube bundles andaggregate structures, which can be rope-like, may offer advantages inhandling, thermal conductivity, electronic properties, and strength.

The strength of the individual carbon nanotubes generated in connectionwith the present invention may be about 30 GPa or more. Strength, asshould be noted, is sensitive to defects. However, the elastic modulusof the carbon nanotubes fabricated in the present invention may not besensitive to defects and can vary from about 1 to about 1.2 TPa.Moreover, the strain to failure of these nanotubes, which generally canbe a structure sensitive parameter, may range from about 5% to a maximumof about 25% in the present invention.

Furthermore, the nanotubes of the present invention can be provided withrelatively small diameter. In an embodiment of the present invention,the nanotubes fabricated in the present invention can be provided with adiameter in a range of from less than 1 nm to about 30 nm. It should beappreciated that the carbon nanotubes made in accordance with oneembodiment of the present invention may be extended in length (i.e.,long tubes) when compared to commercially available carbon nanotubes. Inan embodiment of the present invention, the nanotubes fabricated in thepresent invention can be provided with a length in the millimeter (mm)range, although once coalesced into an extended network of branchedbundles, the unbroken network may extend indefinitely.

It should be noted that although reference is made throughout theapplication to nanotubes synthesized from carbon, other compound(s),such as boron, MoS2, nitrogen or a combination thereof may be used inthe synthesis of nanotubes in connection with the present invention. Forinstance, it should be understood that boron nitride nanotubes may alsobe grown, but with different chemical precursors. In addition, it shouldbe noted that boron and/or nitrogen may also be used to reduceresistivity in individual carbon nanotubes. Furthermore, other methods,such as plasma CVD or the like can also be used to fabricate thenanotubes of the present invention.

CNT member 200 may include any thermally conductive material containingcarbon nanotubes. In an embodiment, CNT member 200 may include anon-woven sheet 210 of nanotubes, a nanotube yarn 220, a woven sheet 230of nanotube yarns, or the like, or any combination thereof, as describedin more detail below.

Non-Woven CNT Sheet 210

Looking now at FIG. 3, the present invention provides, in an embodiment,a non-woven nanostructured CNT sheet 210. The non-woven CNT sheet 210can be so designed to allow thermal conductivity along its length, i.e.,within the plane of the CNT sheet 210. As shown in FIG. 3, the non-wovenCNT sheet 210 may include a substantially planar body having be a singlelayer of a plurality of non-woven carbon nanotubes 14 deposited on topof one another from a cloud of CNT, or alternatively be multiple layers51, each layer being a plurality of non-woven nanotubes deposited on topof one another from a cloud of CNT (see FIG. 4). In case of amultiple-layer sheet, the plurality of non-woven carbon nanotubes formsa layered structure resembling the layers of a phyllo-dough pastry,whereby each layer includes a plurality of non-woven carbon nanotubesdeposited on top of one another from a cloud of CNT.

With reference now to FIG. 5, there is illustrated a system 30, similarto that disclosed in U.S. Pat. No. 7,993,620 (incorporated herein byreference in its entirety for all purposes), for use in the fabricationof nanotubes. System 30, in an embodiment, may be coupled to a synthesischamber 31. The synthesis chamber 31, in general, includes an entranceend 311, into which reaction gases (i.e., gaseous carbon source) may besupplied, a hot zone 312, where synthesis of extended length nanotubes313 may occur, and an exit end 314 from which the products of thereaction, namely the nanotubes and exhaust gases, may exit and becollected. The synthesis chamber 31, in an embodiment, may include aquartz tube 315 extending through a furnace 316. The nanotubes generatedby system 30, on the other hand, may be individual nanotubes, bundles ofsuch nanotubes, and/or intertwined nanotubes. In particular, system 30may be used in the formation of a substantially continuous non-wovensheet generated from compacted and intermingled nanotubes and havingsufficient structural integrity to be handled as a sheet.

System 30, in one embodiment of the present invention, may also includea housing 32 designed to be substantially airtight, so as to minimizethe release of airborne particulates from within the synthesis chamber31 into the environment. The housing 32 may also act to prevent oxygenfrom entering into the system 30 and reaching the synthesis chamber 31.In particular, the presence of oxygen within the synthesis chamber 31can affect the integrity and compromise the production of the nanotubes313. System 30 may also include an injector similar to those disclosedin application Ser. No. 12/140,263, now U.S. Pat. No. 9,061,913, whichis incorporated herein by reference in its entirety for all purposes.

System 30 may also include a moving belt or drum 320 (referred to hereinsimply as belt 320 for simplicity), positioned within housing 32,designed for collecting synthesized nanotubes 313 made from a CVDprocess within synthesis chamber 31 of system 30. In particular, belt320 may be used to permit nanotubes collected thereon to subsequentlyform a substantially continuous extensible structure 321, for instance,a non-woven sheet. Such a sheet may be generated from a matrix ofcompacted, substantially non-aligned, and intermingled nanotubes 313,bundles of nanotubes, or intertwined nanotubes, with sufficientstructural integrity to be handled as a sheet.

To collect the fabricated nanotubes 313, belt 320 may be positionedadjacent the exit end 314 of the synthesis chamber 31 to permit thenanotubes to be deposited on to belt 320. In one embodiment, belt 320may be positioned substantially parallel to the flow of gas from theexit end 314, as illustrated in FIG. 5. Alternatively, belt 320 may bepositioned substantially perpendicular to the flow of gas from the exitend 314 and may be porous in nature to allow the flow of gas carryingthe nanomaterials to pass therethrough, as shown in FIGS. 6A and 6B. Inone embodiment, belt 320 can be designed to translate from side to sidein a direction substantially perpendicular to the flow of gas from theexit end 314, so as to generate a sheet that is substantially wider thanthe exit end 314. Belt 320 may also be designed as a continuous loop,similar to a conventional conveyor belt, such that belt 320 cancontinuously rotate about an axis, whereby multiple substantiallydistinct layers of CNT can be deposited on belt 320 to form a sheet 321,such as that shown in FIG. 4. To that end, belt 320, in an embodiment,may be looped about opposing rotating elements 322 and may be driven bya mechanical device, such as an electric motor. In one embodiment, themechanical device may be controlled through the use of a control system,such as a computer or microprocessor, so that tension and velocity canbe optimized. The deposition of multiple layers of CNT in formation ofsheet 321, in accordance with one embodiment of the present invention,can result in minimizing interlayer contacts between nanotubes.Specifically, nanotubes in each distinct layer of sheet 321 tend not toextend into an adjacent layer of sheet 321. As a result, normal-to-planethermal conductivity can be minimized through sheet 321.

To extent desired, a pressure applicator, such as roller 45, may beemployed. Referring to FIGS. 6A and 6B, the pressure application may besituated adjacent to belt 44, that may be positioned substantiallyperpendicular to the flow of gas, so as to apply a compacting force(i.e., pressure) onto the collected nanomaterials. In particular, as thenanomaterials get transported toward roller 45, the nanomaterials onbelt 44 may be forced to move under and against roller 45, such that apressure may be applied to the intermingled nanomaterials while thenanomaterials get compacted between belt 44 and roller 45 into acoherent substantially-bonded sheet 46. To enhance the pressure againstthe nanomaterials on belt 44, a plate 444 may be positioned behind belt44 to provide a hard surface against which pressure from roller 45 canbe applied. It should be noted that the use of roller 45 may not benecessary should the collected nanomaterials be ample in amount andsufficiently intermingled, such that an adequate number of contact sitesexists to provide the necessary bonding strength to generate the sheet46.

To disengage the sheet 46 of intermingled nanomaterials from belt 44 forsubsequent removal from housing 42, a scalpel or blade 47 may beprovided downstream of the roller 45 with its edge against surface 445of belt 44. In this manner, as sheet 46 moves downstream past roller 45,blade 47 may act to lift the sheet 46 from surface 445 of belt 44. In analternate embodiment, a blade does not have to be in use to remove thesheet 46. Rather, removal of the sheet 46 may be manually by hand or byother known methods in the art.

Additionally, a spool or roller 48 may be provided downstream of blade47, so that the disengaged sheet 46 may subsequently be directedthereonto and wound about roller 48 for harvesting. As the sheet 46 iswound about roller 48, a plurality of layers may be formed. Of course,other mechanisms may be used, so long as the sheet 46 can be collectedfor removal from the housing 42 thereafter. Roller 48, like belt 44, maybe driven, in an embodiment, by a mechanical drive, such as an electricmotor 481, so that its axis of rotation may be substantially transverseto the direction of movement of the sheet 46.

In order to minimize bonding of the sheet 46 to itself as it is beingwound about roller 48, a separation material 49 (see FIGS. 6A and 6B)may be applied onto one side of the sheet 46 prior to the sheet 46 beingwound about roller 48. The separation material 49 for use in connectionwith the present invention may be one of various commercially availablemetal sheets or polymers that can be supplied in a continuous roll 491.To that end, the separation material 49 may be pulled along with thesheet 46 onto roller 48 as sheet 46 is being wound about roller 48. Itshould be noted that the polymer comprising the separation material 49may be provided in a sheet, liquid, or any other form, so long as it canbe applied to one side of sheet 46. Moreover, since the interminglednanotubes within the sheet 46 may contain catalytic nanoparticles of aferromagnetic material, such as Fe, Co, Ni, etc., the separationmaterial 49, in one embodiment, may be a non-magnetic material, e.g.,conducting or otherwise, so as to prevent the sheet 46 from stickingstrongly to the separation material 49. In an alternate embodiment, aseparation material may not be necessary.

After the sheet 46 is generated, it may be left as a sheet 46 or it maybe cut into smaller segments, such as strips. In an embodiment, a lasermay be used to cut the sheet 46 into strips. The laser beam may, in anembodiment, be situated adjacent the housing such that the laser may bedirected at the sheet 46 as it exits the housing. A computer or programmay be employed to control the operation of the laser beam and also thecutting of the strip. In an alternative embodiment, any mechanical meansor other means known in the art may be used to cut the sheet 46 intostrips.

To the extent desired, an electrostatic field (not shown) may beemployed to align the nanotubes, generated from synthesis chamber 31,approximately in a direction of belt motion. The electrostatic field maybe generated, in one embodiment, by placing, for instance, two or moreelectrodes circumferentially about the exit end 314 of synthesis chamber31 and applying a high voltage to the electrodes. The voltage, in anembodiment, can vary from about 10 V to about 100 kV, and preferablyfrom about 4 kV to about 6 kV. If necessary, the electrodes may beshielded with an insulator, such as a small quartz or other suitableinsulator. The presence of the electric field can cause the nanotubesmoving therethrough to substantially align with the field, so as toimpart an alignment of the nanotubes on moving belt.

Alternatively, the carbon nanotubes can be aligned by stretchingfollowing the synthesis of the carbon nanotube sheets as provided inco-pending U.S. application Ser. No. 12/170,092, which is incorporatedherein by reference in its entirety for all purposes.

System 30, as noted, can provide bulk nanomaterials of high strength ina non-woven sheet, as shown in FIG. 4. The carbon nanotubes 14, in anembodiment, can be deposited in multiple distinct layers 51 to from amultilayered structure or morphology in a single CNT sheet 210, as shownin FIG. 4. As noted above, nanofibrous non-woven sheet 210 may be madefrom the deposition of multiple distinct layers of either SWNT or MWNTcarbon nanotubes. In an embodiment, the tensile strength of such anon-woven sheet 210 can be over 40 MPa for SWNT. Moreover, such a sheetmay used with residual catalyst from the formation of the nanotubes.However, typical residuals may be less than 2 atomic percent.

By providing the nanomaterials in a non-woven sheet, the bulknanomaterials can be easily handled while maintaining structuralintegrity and subsequently processed for end use applications. Thesematerials are thermally conductive in-plane, have low thermal mass, arehighly flexible, and are resistant to chemical degradation.

Furthermore, due to the thermal conduction characteristics of carbonnanotubes, the non-woven sheet 210 of the present invention can providethermal protection by being thermally conductive within the plane of thesheet 210, while not being thermally conductive in a directionsubstantially normal to this plane. In particular, in the presence of aheat source, the carbon nanotubes in non-woven sheet 210 may act toconduct heat substantially rapidly away from the heat source, along theplane of the sheet 210, and toward a larger and relatively cooler area,for instance a heat sink. Moreover, because carbon nanotubes can besubstantially resistant to high temperature oxidation, the non-wovensheet 210 made from carbon nanotubes generally can withstand (i.e., doesnot burn) temperature up to about 500° C.

Non-woven CNT sheet 210, in many embodiments, is formed almost entirelyof nanotubes. Nanotube areal densities in various embodiments ofnon-woven sheet 210 may range from about 1 g/m² to about 50 g/m², andpreferably about 10 g/m² to about 20 g/m². In some embodiments, theremay be contaminants, such as iron (residual catalyst) attributable tobetween about 10% to about 15% of the weight of CNT sheet 210.Additionally or alternatively, CNT yarn 200 may include, in addition tothe nanotubes, carbonaceous materials such as soot and polyaromatichydrocarbons. These carbonaceous materials, in some embodiments, may beattributable to about 10% of the weight of CNT sheet 210.

The concentration of carbon nanotubes in non-woven CNT sheet 210 mayvary across embodiments, depending on the desired application; howeverany particular concentration used may be a function of certain keyconsiderations. One such consideration is thermal conductivity—in manyembodiments, non-woven CNT sheet 210 may be provided with a high enoughnanotube concentration to provide a level of thermal conductivitysuitable for wicking away heat from a heat source at a desired rate.Another such consideration is providing sufficient structuralscaffolding for supporting intumescent material 300, and in particular,the foam formed therefrom, as intumescent material 300 undergoes areaction in the presence of heat, as described in more detail below.

CNT Yarn 220

Looking now at FIGS. 7-9, a system 10 similar to system 30 may also beused for manufacturing nanotube yarns. To manufacture yarns, housing 32can be replaced with an apparatus to receive nanotubes from the furnace316 and spin them into yarns. The apparatus may include a rotatingspindle that may collect nanotubes as they exit tube 315. The rotatingspindle may include an intake end into which a plurality of tubes mayenter and be spun into a yarn. The direction of spin may besubstantially transverse to the direction of movement of the nanotubesthrough tube 315. Rotating spindle may also include a pathway alongwhich the yarn may be guided toward an outlet end of the spindle. Theyarn may then be collected on a spool. System 10 may be similar to thatdisclosed in application Ser. No. 11/488,387, now U.S. Pat. No.7,993,620, which is hereby incorporated herein by reference in itsentirety for all purposes.

Rotating spindle 14, as shown in FIG. 7, may be designed to extend fromwithin housing 12, through inlet 13, and into synthesis chamber 11 forcollection of extended length nanotubes 113. In an embodiment, rotatingspindle 14 may include an intake end 141 into which a plurality ofnanotubes may enter and be spun into a yarn 220. In an embodiment, thedirection of spin may be substantially transverse to the direction ofmovement of the nanotubes 113. Rotating spindle 14 may also include apathway, such as hollow core 142, along which yarn 220 may be guidedtoward outlet end 143 of spindle 14. The intake end 141 of rotatingspindle 14 may include a variety of designs. In one embodiment, intakeend 141 may simply include an aperture (not shown) through which thenanotubes 113 may enter. Alternatively, it may include a funnel-likestructure 144 that may serve to guide the nanotubes 113 into the intakeend 141. Structure 144 can also serve to support yarn 220, should itbreak, until such time that it might be able to reconstitute itself fromthe twisting with newly deposited nanotubes 113. In one embodiment, aroller, capstan or other restrictive devices+ (not shown) may beprovided adjacent the intake end 141 of spindle 14 in order to: (1)serve as a point from which yarn 220 may be twisted, and (2) preventspringiness in yarn 220 from pulling the yarn too quickly into the core142 of spindle 14, which can prevent yarn 220 from re-forming if it wereto break.

System 10 further includes a guide arm 16 which may be coupled to theoutlet end 143 of rotating spindle 14 to guide and direct yarn 220toward a spool 17 for gathering thereon. In accordance with oneembodiment of the present invention, a set of pulleys 161, eyelets, orhooks may be provided as attachments to the guide arm 16 to define apath on which yarn 220 may be directed along the guide arm 16.Alternatively, yarn 220 may be permitted to pass through a tubularstructure (not shown) that can direct yarn 220 from the outlet end 143of spindle 14 to a point from which yarn 220 may be wound onto spool 17.

Guide arm 16 and rotating spindle 14, in an embodiment, may worktogether to induce twisting in yarn 220. The rotation of spindle 14 andguide arm 16 may be mechanically driven, for example, by an electricmotor 18 coupled to the spindle 14 via a belt 181, for instance.

Spool 17, situated within housing 12, may be positioned, in oneembodiment, downstream of guide arm 16 for the harvesting of yarn 220.In particular, yarn 220 advancing from guide arm 16 may be directed onto a spinning spool 17, such that yarn 220 may thereafter be woundcircumferentially about spool 17. Although shown to be in axialalignment with rotating spindle 14, it should be appreciated that spool17 may be placed at any other location within housing 12, so long asspool 17 may be spun about its axis to collect yarn 220 from guide arm16. In an embodiment the axis of spin of spool 17 may be substantiallytransverse to the direction of movement of yarn 220 onto spool 17.

To impart rotation to spool 17, an additional mechanical drive 19 may becoupled to spool 17. In one embodiment, spool 17 may be synchronized tospin or rotate near or at substantially a similar rotation rate as thatof spindle 14 to permit uniform harvesting of yarn 220 on to spool 17.Otherwise, if, for instance, the rate of rotation of spool 17 is fasterthan that of spindle 14, breakage of yarn 220 from guide arm 16 to spool17 may occur, or if the rate is slower than that of spindle 14, looseportions from yarn 220 may end up entangled.

To maintain substantial synchronization of rotation rates, movement ofmechanical drives 18 and 19 may be adjusted by a control system (notshown). In one embodiment, the control system may be designed to receivedata from position sensors, such as optical encoders 182, attached toeach of mechanical drives 17 and 18. Subsequently, based on the data,the control system may use a control algorithm in order to modify powersupplied to each drive in order to control the rate of each drive sothat they substantially match the rate of nanotube synthesis. As aresult, the control system can impart: (1) constant yarn velocitycontrolled by set tension limits, or (2) constant tension controlled byvelocity limits. In one embodiment, the yarn velocity can be reset inreal time depending on the tension values, so that the tension may bekept within a preset limit. In addition, the yarn tension can be resetin real time depending on the velocity values, so that the tension canbe kept within a set value.

The control system can also vary the rate between the spool 17 andspindle 14, if necessary, to control the yarn up-take by the spool 17.In addition, the control system can cause the spool 17 to move back andforth along its axis, so as to permit the yarn 220 to be uniformly woundthereabout.

In operation, under steady-state production using a CVD process of thepresent invention, extended length nanotubes may be collected fromwithin the synthesis chamber 11 and yarn 220 may thereafter be formed.In particular, as the nanotubes 113 emerge from the synthesis chamber11, they may be collected into a bundle, fed into the intake end 141 ofspindle 14, and subsequently spun or twist into yarn 220 therewithin. Itshould be noted that a continual twist to yarn 220 can build upsufficient angular stress to cause rotation near a point where newnanotubes 113 arrive at the spindle 14 to further the yarn formationprocess. Moreover, a continual tension may be applied to yarn 220 or itsadvancement may be permitted at a controlled rate, so as to allow itsuptake circumferentially about spool 17.

Typically, the formation of yarn 220 results from a bundling ofnanotubes 113 that may subsequently be tightly spun into a twistingyarn. Alternatively, a main twist of yarn 220 may be anchored at somepoint within system 10 and the collected nanotubes 113 may be wound onto the twisting yarn 220. Both of these growth modes can be implementedin connection with the present invention.

Looking now at FIG. 8, a vortex generator, such as gas-spinner 20, maybe provided toward the exit end 114 of synthesis chamber 11 to generatea substantial vortex flow in order to impart a twisting motion to thenanotubes 113 prior to being directed into spindle 14 and spun into yarn220. The generation of a vortex to impart twisting motion may also serveto even out an amount of nanotube material used in the formation of yarn220.

It should also be appreciated that by providing a solid constriction tothe flow of gas and generated nanomaterials, the gas-spinner 20 can alsoallow substantial freedom in defining yarn and tow formation modes forsystem 10 of the present invention. Moreover, to the extent necessary,gas-spinner 20 can provide an area where nanotubes 113 may accumulate,particularly when the gas supplied through the gas-spinner 20 is at alow flow rate to create a source from which nanotubes 113 may be pulled,such as that by a leader (see description below) to subsequently twistinto yarn 220.

In accordance with one embodiment of the present invention, at theinception of formation of yarn 220, it may be beneficial to start theyarn with a “leader.” This leader, for example, may be an additionalpiece of nanotube yarn, some other type of yarn or filament, or a thinwire. In an embodiment, a wire may be used because it can provide therequisite stiffness necessary to transfer the twisting motion of thespindle 14 to the accumulating webbing or bundle of nanotubes 113 untilthere exist a sufficient build-up, such that the wire can tether an endof a growing yarn. The wire used, in one embodiment, may be, forexample, a ferrous wire or Nichrome, since these alloys can withstandthe temperature within the hot zone (600° C.-1300° C.) of the synthesischamber 11. Moreover, nanotubes produced via a CVD process have beenobserved to adhere relatively well to these alloys. In particular, sincecatalytic nanoparticles at the end of the nanotubes 113 may includeferromagnetic materials, such as Fe, Co, Ni, etc., these nanoparticlescan magnetically attract to the magnetic domains on the ferrous alloymaterials.

To the extent that a leader is provided, it may be necessary topre-thread the leader before the start of the reaction. Specifically, ahole, in one embodiment, may provided in the spool 17 to serve as ananchor point for one end of the leader. Additionally, notches or slotsmay be provided in the guide pulleys 161 to permit the leader to beeasily inserted into the guide arm 16. The leader may then be insertedinto the spindle 14, and thereafter advanced into the synthesis chamber11 upstream to gas-spinner 20, should one be employed.

Looking at FIG. 9, when using a leader, an anchor 40 may be provided inplace of gas-spinner 20 to provide a source from which the leader canpull nanotubes into the spindle 14 to initiate the yarn making process.In an embodiment, anchor 40 may be positioned toward the exit end 114 ofsynthesis chamber 11 to constrict the flow of gas and nanotubes 113 sothat an accumulation of nanotubes 113 can be generated within the anchor40. To do so, anchor 40 may be designed as a disc having a distal end41, a proximal end 42, and a passageway 44 extending therebetween. Asillustrated in FIG. 6, passageway 44 may taper from the proximal end 42toward the distal end 41. In this manner, when nanotubes 113 enterpassageway 44 toward constricted portion 45, the constricted portion 45may act to accumulate nanotubes 113 thereat to provide a source for theleader. Although provided as being tapered or toroidal in shape, itshould be appreciated that passageway 44 of anchor 40 may be designed toinclude a variety of forms, so long as it works to constrict the flow ofgas and nanotubes 113 in chamber 11.

To enhance the accumulation of nanotubes there at, projections (notshown) or other similar designs may be provided at the constrictedportion 45 to provide a surface to which a webbing or bundle ofnanotubes 113 can attach. In one embodiment, anchor 40 can be positionednear furnace 116 where the nanotubes 113 may have a relatively greatertendency to adhere to solid surfaces. As it may be near furnace 16,anchor 40 may be made, in an embodiment, from a graphite material or anyother material that would withstanding heat from furnace 16.

Assuming that the nanotubes 113 can be produced at a constant rate, thedesign and location of anchor 40 near furnace 116 can permit thenanotubes 113 to accumulate thereon at a uniform rate. To that end, acontrolled source of nanotubes 113 may be generated for subsequentcollection and formation of yarn 220 having substantially uniformproperties. Furthermore, anchor 40 can act to provide a point from whichthe nanotubes 113 can be pulled to permit substantial alignment of thenanotubes 113 in a direction substantially coaxial with yarn 220. Theability to align the nanotubes 113 along an axis of yarn 220 can enhanceload transfer between the nanotubes 113 to allow for the formation of ahigh strength yarn 220. Nevertheless, it should be appreciated that yarn220 can be formed regardless of whether anchor 40 is present.

Synthesis and harvesting of yarn 220 may subsequently be initiated bycausing the spool 17, spindle 14, guide arm 16, and leader to rotate. Inone embodiment, after initiating the synthesis of nanotubes 113, thenanotubes 113 may be directed toward the leader to permit build-up orbundling of the nanotubes 113 thereon. Thereafter, once a webbing orbundling of nanotubes 113 begins to build up on the leader, and theleader can be withdrawn by causing the spool 17 to rotate at a slightlydifferent rate than the spindle 14 and guide arm 16. The formation ofthe nanotube yarn 220, as described above, may proceed automaticallythereafter once the leader has been withdrawn sufficiently from the hotzone 112 of synthesis chamber 11. In particular, the webbing ofnanotubes 113 may be twisted into a yarn 220 at a point near the intakeend 141 of spindle 14. The twisted portions of yarn 220 may then beallowed to move along the core 142 towards the outlet end 143 of spindle14. Upon exiting the outlet end 143, the yarn 220 may be guided alongguide arm 16 and directed toward the spool 17. The yarn 220 maythereafter be wound about spool 17 at a controlled rate.

In accordance with another embodiment, the system 10 may also be usedfor continuous formation of a tow (not shown) from nanotubes 113synthesized within synthesis chamber 11. This tow may be later processedinto a tightly wound yarn, similar to technologies common in the art ofthread and yarn formation. In one embodiment, the tow may be collectedusing the hollow spindle 14, guide arm 16 and spool 17, as describedabove. The formed tow may extend from the spool 17, through the guidearm 16 and spindle 14 into the synthesis chamber 11 near the exit end114. Nanotubes 113, in an embodiment, may accumulate on the tow bywinding around the tow, as the tow spins rapidly and is slowlywithdrawn. An anchor may not required for this mode of operation.However, should it be necessary to provide a point to which the growingend of the spinning tow may attach, an anchor may be used.

The formation of a yarn or tow in accordance with one embodiment of thepresent invention provides an approach to producing a relatively longfibrous structure capable of being employed in applications requiringlength. In particular, the twisting action during formation of the yarnallows the staple fibers (i.e., nanotubes) to be held together into thelarger fibrous structure (i.e., yarn). Additionally, the twisting ofaxially aligned fibers (i.e., nanotubes) can enhance load transferbetween the fibers to allow for the formation of a high strength yarn.

Specifically, staple fibers, such as the nanotubes synthesized by theprocess of the present invention, can be provided with a high aspectratio (e.g., >100:1 length:diameter). As a result, they can serve betterthan those with smaller aspect ratios to transfer structural loadsbetween individual fibers within a yarn. While fibers with essentiallyinfinite aspect ratio would be ideal, the length scale of structures inwhich the yarn may be incorporated better defines the length and aspectratios required of the constituent fibers. For example, if it isnecessary to bridge a distance of only one to two centimeters, fibersmuch longer than this distance may not required. Furthermore, within ayarn, load transfer typically occurs as an interaction between each ofthe contact points of adjacent fibers. At each contact point, each fibermay interact via, for example, a van der Waal's bond, hydrogen bond, orionic interaction. As such, the presence of a plurality of fibers in theyarn of the present invention can increase the number of contact pointsand thus the bonding interaction between adjacent fibers to enhance loadtransfer between the fibers. Moreover, since twisting can furtherincrease the number of contact points between constituent fibers in ayarn by forcing individual fibers closer together, it can beadvantageous to the overall strength of the yarn to impart twisting. Inthis regard, the ability to independently control twisting and up-takevelocity can be important in order to optimize strength.

The strength of the yarn can further be enhanced by increasing the bondstrength between adjacent fibers. In one embodiment, the yarn may beimpregnated with a matrix material, such as a polymer, or a surfactantmolecule to crosslink adjacent fibers. Crosslinking the fibers usingcovalent or ionic chemical bonds can provide an additional means ofimproving the overall strength of the yarn.

It should be noted that since the number of contact points increases theopportunities for phonon or electron to transfer between adjacentnanotubes, the imparting of a twist to the yarn can also enhance theelectrical and thermal conductivity of the yarn of the presentinvention. In the presence of a heat source, the carbon nanotubes inyarn 220 may act to conduct heat substantially rapidly away from theheat source, along the length of the yarn 220, and toward a larger andrelatively cooler area, for instance a heat sink.

CNT yarn 220, in many embodiments, is formed almost entirely ofnanotubes. Nanotube linear densities in various embodiments of CNT yarn220 may range from about 0.5 Tex (g/km) to about 100 Tex or higher. Insome embodiments, there may be contaminants, such as iron (residualcatalyst) attributable to between about 10% to about 15% of the weightof CNT yarn 220. Additionally or alternatively, CNT yarn 220 mayinclude, in addition to the nanotubes, carbonaceous materials such assoot and polyaromatic hydrocarbons. These carbonaceous materials, insome embodiments, may be attributable to about 10% of the weight of CNTyarn 220.

The concentration of carbon nanotubes in CNT yarn 220 may vary acrossembodiments, depending on the desired application; however anyparticular concentration used may be a function of certain keyconsiderations. One such consideration is thermal conductivity—in manyembodiments, CNT yarn 220 may be provided with a high enough nanotubeconcentration to provide a level of thermal conductivity suitable forwicking away heat from a heat source at a desired rate. Another suchconsideration is providing sufficient structural scaffolding forsupporting intumescent material 300, and in particular, the foam formedtherefrom, as intumescent material 300 undergoes a reaction in thepresence of heat, as described in more detail below.

Woven CNT Sheet 230

In another embodiment of the present disclosure, CNT member 200 mayinclude a woven CNT sheet 230 formed by weaving together, braiding,knitting, or otherwise combining in like manner multiple carbon nanotubeyarns 220. Like non-woven CNT 210 and CNT yarns 220, woven CNT sheet 230may exhibit good in-plane thermal conductivity, thereby helping todissipate heat away from hot spots in an in-plane direction whilstminimizing through-plane heat transfer. Without wishing to be bound bytheory, thermal energy may follow the independent conduction pathwaysform by each CNT yarns 220 woven into woven CNT sheet 230, carrying heataway from a hot spot in the X- and Y-directions with which the CNT yarns220 are aligned. Woven CNT sheet 230, owing to the high strength of CNTyarns 220 from which it is made, may exhibit very high tensile strengthsrelative to non-woven sheets.

In yet another embodiment, CNT member 200 may be a composite articlecomprising woven CNT sheet 230 placed in contact with a non-woven CNTsheet 210. Such a configuration may exhibit the favorablecharacteristics of sheets 210 and 230. For example, in the compositearticle, woven CNT sheet 230 may contribute superior strength andthermal conductivity to the composite article, and non-woven CNT sheet210 may contribute greater surface area and different microstructure.Intumescent material 300, in various embodiments, could be introducedinto the yarns of woven CNT sheet 230, into the interstices between theyarns woven CNT sheet 230, into non-woven CNT sheet 210, or anycombination thereof.

CNT Network 240

In yet another embodiment of the present disclosure, CNT member 200 maytake the form of a CNT network 240. Generally speaking, CNT network 240is formed by drying a solution of dispersed carbon nanotubes in asolvent. CNT network 240, in some embodiments, may further include oneor more additives such as, without limitation, surfactants (forenhancing uniformity with which the nanotubes are distributed throughoutthe solution used to form the network), acids (for same purpose, as wellas functionalizing the nanotubes), binder (for increasing viscosity ofthe solution and holding the various components of the networktogether). As later discussed in more detail, in an embodiment ofintumescent nanostructured material 100, intumescent material 300 may bemixed into the solution used to form CNT network 240 to provide enhancedthermal protection capabilities. The resulting solution ofnanostructured materials, intumescent material 300, and solvent may becoated or sprayed onto a surface and dried to form athermally-protective coating (an embodiment of intumescentnanostructured material 100) including CNT network 240 and intumescentmaterial 300, as later described in more detail.

The solution of nanostructured materials may be prepared according toany suitable method known in the art. Representative methods for formingthe solution may be found in U.S. patent application Ser. No.15/351,912, which is hereby incorporated by reference in its entiretyfor all purposes.

The concentration of nanostructured materials in the solution may varyacross embodiments, depending on the desired application; however anyparticular concentration used may be a function of certain keyconsiderations. One such consideration is thermal conductivity—in manyembodiments, the solution may be provided with a high enough nanotubeconcentration to provide a level of thermal conductivity suitable forwicking away heat from a heat source at a desired rate. Another suchconsideration is providing sufficient structural scaffolding forsupporting intumescent material 300 in CNT network 240, and inparticular, the foam formed therefrom, as intumescent material 300undergoes a reaction in the presence of heat, as described in moredetail below. In various embodiments, the solution, in furtherance ofthese considerations, may contain carbon nanotubes in concentrationsranging from about 1% to about 80%, and preferably around 10% by volume.

Intumescent Material 300

Embodiments of intumescent nanostructured material 100 further includeone or more intumescent materials 300 for enhancing thermal protection.When exposed to heat, intumescent materials undergo chemical reactionsthat results in the formation of a foam that insulates material 100 fromfurther heat exposure and oxygen. During the reaction, heat energy isabsorbed as hydrates boil and water vapor is released, thereby providinga cooling effect as the energy of vaporization is consumed. For ageneral frame of reference, many intumescent materials may undergoreaction and form the foam when exposed to temperatures of about 400° C.or greater.

Intumescent material 300 may include any suitable material thatundergoes such an endothermic chemical reaction resulting in theformation of an insulating foam or similar material. Example intumescentmaterials include, without limitation, soft char (e.g., ammoniumpolyphosphate, pentaeyrthritol, and melamine in a binder of vinylacetate or styrene acrylates) and hard char (e.g., sodium silicates,graphite). Intumescent material 300 may further include or be combinedwith a binder (e.g., various polymeric resins) for bonding material 300to other materials, a blowing agent (e.g., melamine or urea) thatthermally decomposes to produce gasses to facilitate formation of theintumescent foam, and/or fire-proofing agents (e.g., boric acid, borax,zinc borate, silazanes, ammonium polyphosphate) for preventing oxidationof materials in contact with intumescent material 300 (e.g., CNTs). Ofcourse, any suitable intumescent material with the properties describedherein is envisioned within the scope of the present disclosure.Intumescent material 300, in various embodiments, may be applied to CNTmember 200 in any suitable manner. In an embodiment, intumescentmaterial 300 may be dissolved in an appropriate solvent, rinsed into CNTmember 200, which may then be dried to remove the solvent. Additionaldetails are provided in Examples 1-8 below.

Synergies between CNT member 200 and intumescent 300 may allow for thecreation of thicker foams with closed-cell morphologies as compared withthose foams formed from intumescents included in polymer matrices. Inone aspect, the high densities of carbon nanotubes included in CNTmember 200 provide ample scaffolding for supporting the foam as it formssuch that the cells of the foam are less likely to pop and collapse. Asconfigured, the foam can grow thicker and retain a highly-insultingclosed-cell morphology. Generally speaking, the synergies between CNTmember 200 and intumescent 300 can be expected to lead to the generationof foams having smaller, stronger cells as compared to unsupportedintumescents or intumescents mixed with non-CNT materials. Withoutwishing to be bound by theory, it is thought that the strength impartedby CNT member 200 reinforces the closed cells of the foam, causingsmaller, more stable cells to form.

Ceramifying Polymer Material 400

Embodiments of intumescent material 100 can additionally be coated orimpregnated with a ceramifying polymer material 400 to enhance thestrength of the CNT member 200 and its oxidation resistancecharacteristics. Example ceramifying polymer materials include, withoutlimitation, polysilazane, polyureasilazane (PSZ), andPolyureamethylvinylsilazane Ceraset® (Kion Corporation, HuntingdonValley, Pa.). For simplicity, ceramifying polymer material 400 may bereferred to herein as PSZ 400; however, it should be understood that thepresent disclosure is not intended to limit ceramifying polymer material400 to only this embodiment. PSZ resin 400 may react with heat to form aheat-resistant ceramic coating on the carbon nanotubes of CNT member200. This ceramic coating may help prevent or otherwise reduce thermaldegradation or burning of the carbon nanotubes when exposed to highlevels of heat, thereby improving the overall structural integrity ofmaterial 100 and its ability to provide thermal protection.

In some embodiments, PSZ 400 may be coated onto or impregnated intonon-woven sheet 210, yarn 220, and woven sheet 230. To form the coatingmaterial, the PSZ 400 400 may be dissolved in acetone solutions inconcentrations ranging from about 0.1% to about 20%, preferable around3% by weight. Next, the solution may be coated onto the CNT member 200,and then allowed to air dry. Thereafter, the coated CNT member 200 maybe hot pressed at an elevated temperature ranging from about 50° C. toabout 300° C., and preferably around 200° C., for about 120 minutes. Thepressure at which the hot pressing may be carried out can range fromabout 14.7 psi to about 20,000 psi. After hot-pressing, the resultingcoated CNT member 200 may be ready to use. In some embodiments, PSZ 400may be attributable to about 5% to about 80% of the weight of the PSZ400-coated CNT member 200 (before application of intumescent material300), and preferably about 20% to about 30% of the weight of the PSZ400-coated CNT member 200 (before application of intumescent material300).

The strength of this coated CNT member 200 can be increased as a resultof this process from about 30 MPa to over about 300 MPa. In addition,exposure of the PSZ 400 coated CNT member 200 to a MAAP flame does notresults in burning of the material. Rather, the silazane is converted tosilicon oxide and most probably forms regions of well-bonded siliconcarboid locking the structure together. In one embodiment, a CNT member200 coated with PSZ 400 can withstand heat over 1000° C. or higherwithout burning for several minutes.

Interestingly, traditional non-CNT textiles treated with PSZ 400 saw nosuch benefits in testing.

PSZ 400 can also be included in varying concentrations in the solutionused to form CNT network 240. In representative embodiments, PSZ 400 maybe added in suitable concentrations to the solution such that PSZ 400accounts for about 2% to about 50%, and preferably about 25%, of the dryweight of CNT network 240. Without wishing to be bound by theory, thePSZ 400 may exhibit certain synergies with intumescent material 300,beyond simply forming a protective ceramic coating around the nanotubes.In particular, PSZ 400 may undergo an endothermic reaction as itthermally decomposes, thus providing further thermal protection forintumescent nanostructured material 100 and the persons, animals, orobjects it protects.

Additional Treatments

Intumescent nanostructured materials 100 of the present invention, invarious embodiments, may be further treated to improve its mechanicalintegrity and/or thermal performance. In one such embodiment, material100 may be coated and/or infiltrated with a polymer(s), which mayprotect the material from water, humidity and weather, as well aspossibly affect the formation of the foam as intumescent material 300undergoes endothermic reaction. Example polymers suitable for thesepurposes include, without limitation, PVC, EPDM, and Aramids. In anembodiment, these polymers may be added via dissolved monomers, oroligomers added together and reacted once infiltration is complete.Additionally or alternatively, in another embodiment, intumescentnanostructured material 100 may be coated and/or infiltrated with aflame retardant chemical(s), such as boric acid, borax, zinc borate,ammonium polyphosphate (APP), or any combination thereof. Testing hasshown particularly favorable synergies between boric acid and APP, forexample.

Example 1

Embodiments of an intumescent nanostructured material 110 may includenon-woven CNT sheet 210, intumescent material 300, and ceramifyingpolymer 400. Depending on the particular embodiment, non-woven CNT sheet210 may account for about 10% to about 50% of the dry weight ofintumescent nanostructured material 110, intumescent material 300 mayaccount for about 0% to about 70% of the dry weight of intumescentnanostructured material 110, and ceramifying polymer material 400 mayaccount for about 25% of the dry weight of intumescent nanostructuredmaterial 110. In some embodiments, intumescent nanostructured material110 may further include binder (e.g., vinyl acetate, styrene acrylatesor polyurethane), which may account for about 3% to about 50% of the dryweight of intumescent nanostructured material 110. Additionally oralternatively, some embodiments of intumescent nanostructured material110 may include flame retardant material(s) (e.g., boric acid), whichmay account for about 5% of the dry weight of intumescent nanostructuredmaterial 110.

Example 2

The intumescent nanostructured material 110 of Example 1 may be coatedwith intumescent material 140 (later described in Example 8) to formintumescent material 112. In some embodiments, a composite 114 may beformed by building up multiple layers of intumescent material 112 forenhanced thermal protection.

Example 3

Embodiments of an intumescent nanostructured material 120 may includeCNT yarn 220, intumescent material 300, and ceramifying polymer 400.Depending on the particular embodiment, CNT yarn 220 may account forabout 10% to about 90% of the dry weight of intumescent nanostructuredmaterial 120, intumescent material 300 may account for about 0% to about50% of the dry weight of intumescent nanostructured material 120, andceramifying polymer material 400 may account for about 30% of the dryweight of intumescent nanostructured material 120. In some embodiments,intumescent nanostructured material 120 may further include binder(e.g., vinyl acetate or styrene acrylates), which may account for about0% to about 50% of the dry weight of intumescent nanostructured material120. Additionally or alternatively, some embodiments of intumescentnanostructured material 120 may include flame retardant material(s)(e.g., boric acid), which may account for about 5% of the dry weight ofintumescent nanostructured material 120.

Example 4

The intumescent nanostructured material 120 of Example 3 may be coatedwith intumescent material 140 (later described in Example 8) to formintumescent material 122. In some embodiments, a composite 124 may beformed by building up multiple layers of intumescent material 122 (e.g.,twisting multiple yarns to form a wire or rope) for enhanced thermalprotection.

Example 5

Embodiments of an intumescent nanostructured material 130 may includewoven CNT sheet 230, intumescent material 300, and ceramifying polymer400. Depending on the particular embodiment, non-woven CNT sheet 230 mayaccount for about 0% to about 50% of the dry weight of intumescentnanostructured material 130, intumescent material 300 may account forabout 10% to about 80% of the dry weight of intumescent nanostructuredmaterial 130, and ceramifying polymer material 400 may account for about30% of the dry weight of intumescent nanostructured material 130. Insome embodiments, intumescent nanostructured material 130 may furtherinclude flame retardant material(s) (e.g., boric acid), which mayaccount for about 5% of the dry weight of intumescent nanostructuredmaterial 130.

Example 6

The intumescent nanostructured material 130 of Example 5 may be coatedwith intumescent material 140 (later described in Example 8) to formintumescent material 132. In some embodiments, a composite 134 may beformed by building up multiple layers of intumescent material 132 forenhanced thermal protection.

Example 7

The intumescent nanostructured material 132 or composite 134 of Example6 may be overlaid with a non-woven CNT sheet 210 or intumescent material110 to form intumescent material 136. In some embodiments, a composite138 may be formed by building up multiple layers of intumescent material136 for enhanced thermal protection.

Example 8

Embodiments of a thermally-protective coating 140 (also referred toherein as intumescent nanostructured material 140) may include CNTnetwork 240, intumescent material 300, and ceramifying polymer 400.Depending on the particular embodiment, CNT network 240 may account forabout 1% to about 10% of the dry weight of intumescent nanostructuredmaterial 140, intumescent material 300 may account for about 0% to about70% of the dry weight of intumescent nanostructured material 140, andceramifying polymer material 400 may account for about 25% of the dryweight of intumescent nanostructured material 140. In some embodiments,intumescent nanostructured material 140 may further include binder(e.g., vinyl acetate or styrene acrylates), which may account for about3% to about 10% of the dry weight of intumescent nanostructured material140. Additionally or alternatively, some embodiments of intumescentnanostructured material 140 may include flame retardant material(s)(e.g., boric acid), which may account for about 5% of the dry weight ofintumescent nanostructured material 140. Solvent (e.g., acetone,xylenes, 1-methyl pyrholidone) may be used to adjust the viscosity ofintumescent nanostructured material 140 to be suitable for layering orspraying. For example, solvent may be utilized to adjust the viscosityof intumescent nanostructured material 140 to about 3000 centipoise toabout 6000 centipoise for coating/layering, and to about less than 1000centipoise for spraying.

In one representative embodiment, intumescent nanostructured material140 may be formed by rinsing a nanotube pulp in an about 2% to about 20%solution of ceramifying polymer 400 (e.g., Ceraset monomer) in acetone.The rinsed nanotube pulp may then be dried in an oven, for example, atabout 100° C. for about 30 minutes to dry the ceramifying polymer 400 onthe nanotubes. The coated nanotube pulp may be further baked to solidifythe ceramifying polymer 400, for example, at about 200° C. for about 1hour. The nanotubes now include a ceramifying polymer coating foradditional protection.

Next, the nanotube pulp may be combined with intumescent material 300(e.g., soft char, hard char), and any combination of binder, flameretardant, and solvent to create a viscous solution. The solution may bemixed in a high shear mixer until the nanotube pulp and intumescentmaterial 300 are fully dispersed. The solution may then be diluted untilit is the proper viscosity for coating/layering, spraying, or othersuitable application.

In an embodiment, the solution may be mixed into liquid paint forcoating or spraying onto an object for thermal protection. For example,about 2.5 g of coated nanotube pulp may be mixed well with about 100 gacrylic paint, along with about 5 g of boric acid, about 5 g of ammoniumpolyophosphate, and about 2.5 g of melamine. This may be diluted with 5%ethanol in water until a viscosity suitable for spraying is obtained.The viscous mixture is then ready for spraying on an object to providethermal protection. Other suitable paints may include, withoutlimitation, polyurethane- and oil-based paints.

Articles Made from Intumescent Nanostructured Material 100

Intumescent nanostructured material 100 may be used in a variety ofpractical applications, and in particular, for thermal protection andfire protection. For example, embodiments of material 100 formed fromnon-woven sheets 210 or woven sheets 230 may be integrated into or usedas textiles, such as, without limitation, in fire blankets, firefightersuits, and fire-protective clothing for race car drivers, pilots, andthe like. Similarly, embodiments of material 100 including yarn s 220may be used in such textiles, as well as in other applications such asin cables and wires that may operate in hot environments or in closeproximity to heat sources. Each may also be used in structures likefire-resistant or heat tolerant housings around heat sources likeengines and heaters, or to surround things needing protection in anotherwise hot environment. Camping tents, awnings, and other structuresoften situated near flames or hot lamps may similarly benefit fromincorporation of material 100.

The solution may be used to form thermally-protective layers 140 oncomponents requiring thermal or fire protection. For example, thesolution may be spray coated onto surfaces of I-beams and otherstructural members in buildings and vehicles and dried to formintumescent nanostructured material 140 thereon, which may prevent ordelay weakening and ultimate collapse of the structure in the event of afire. Further, the solution may be sprayed onto a substrate, dried, andpeeled off as a sheet for similar applications as those listed above.The same may be done with the solution by filtering or molding thesolution or CNT pulp to form a buckypaper-like form of intumescentnanostructured material 100. Such embodiments may be used in wayssimilar to sheets 210, 230 as described above. Additionally oralternatively, the solution could be coated onto and/or infiltrated intonon-woven CNT sheet 210, CNT yarn 220, woven CNT sheet 230, or anycombination thereof.

In still further embodiments, intumescent nanostructured material 100may be applied to the back of a CNT heating element to provide alow-mass, fireproof insulating layer to keep the thermal energy of theheating elements from being conducted away from the target to be heated.Similarly, an integrated CNT heater and insulator backing may be formedby backing a CNT sheet or woven CNT yarn with intumescent nanostructuredmaterial 140 and appropriate additives. Such an article may be thermallyprocessed at high temperature to create a stable heater with anintegrated, flexible, insulated backing.

Of course, these are merely illustrative examples, and one of ordinaryskill in the art may recognize further practical applications of variousembodiments of intumescent nanostructured material 100 within the scopeof the present disclosure.

While the present invention has been described with reference to certainembodiments thereof, it should be understood by those skilled in the artthat various changes may be made and equivalents may be substitutedwithout departing from the true spirit and scope of the invention. Inaddition, many modifications may be made to adapt to a particularsituation, indication, material and composition of matter, process stepor steps, without departing from the spirit and scope of the presentinvention. All such modifications are intended to be within the scope ofthe claims appended hereto.

What is claimed is:
 1. An intumescent nanostructured material for thermal protection, comprising: a member coated or impregnated with a ceramifying polymer material comprising a silazane and including a plurality of nanostructured materials comprising a combination of graphene and nanotubes having a diameter ranging from 1 to 30 nm and an aspect ratio of length to diameter greater than 100:1, wherein the member contains residual iron in an amount up to 15 wt % based on the total weight of member; and an intumescent material associated with the member, and configured to react in the presence of a heat source to form a foam for thermally insulating the member from the heat source, wherein the intumescent nanostructured material is coated with one or more of polyvinyl chloride, EPDM, and an aramid.
 2. An intumescent nanostructured material as set forth in claim 1, wherein the member is a non-woven sheet, a woven sheet, a yarn, or a network.
 3. An intumescent nanostructured material as set forth in claim 1, wherein the intumescent material includes soft char, hard char, or a combination thereof.
 4. An intumescent nanostructured material as set forth in claim 3, wherein the soft char includes one or a combination of ammonium polyphosphate, pentaeyrthritol, and melamine in a binder of vinyl acetate or styrene acrylates.
 5. An intumescent nanostructured material as set forth in claim 3, wherein the hard char includes one or a combination of sodium silicate or graphite.
 6. An intumescent nanostructured material as set forth in claim 1, wherein the intumescent material is combined with a blowing agent that thermally decomposes to produce gasses to facilitate formation of the foam.
 7. An intumescent nanostructured material as set forth in claim 1, wherein the intumescent material is coated onto, infiltrated into, or mixed with the member.
 8. An intumescent nanostructured material as set forth in claim 1, wherein the intumescent material reacts to form the foam at temperatures at or above about 400° C.
 9. An intumescent nanostructured material as set forth in claim 1, further including a flame retardant for protecting the nanostructured materials from oxidation in the presence of the heat source.
 10. An intumescent nanostructured material for thermal protection, comprising: a non-woven member coated or impregnated with a ceramifying polymer material comprising a silazane and having a plurality of layers of intermingled and compacted nanotubes having a diameter ranging from 1 to 30 nm and an aspect ratio of length to diameter greater than 100:1 and graphene, and wherein some of the nanotubes between adjacent layers are intermingled with one another such that an adequate number of contact sites exists to bond the adjacent layers together and wherein the non-woven member contains residual iron in an amount up to 15 wt % based on the total weight of the non-woven member; and an intumescent material coated onto the non-woven member, and configured to react in the presence of heat to form a foam, wherein the non-woven member is configured to provide in-plane thermal conductivity while minimizing through-plane thermal conductivity, wherein the intumescent nanostructured material is coated with one or more of polyvinyl chloride, EPDM, and an aramid.
 11. An intumescent nanostructured material as set forth in claim 10, wherein the non-woven member has a nanotube areal density of about 20 g/m² to about 30 g/m².
 12. An intumescent nanostructured material as set forth in claim 10, wherein the nanotubes act as scaffolding for accommodating and holding the intumescent material in place.
 13. An intumescent nanostructured material as set forth in claim 10, wherein the nanotubes promote the foam to form with a substantially closed-cell structure.
 14. An intumescent nanostructured material as set forth in claim 10, wherein the intumescent material includes soft char, hard char, or a combination thereof.
 15. An intumescent nanostructured material as set forth in claim 14, wherein the soft char includes one or a combination of ammonium polyphosphate, pentaeyrthritol, and melamine in a binder of vinyl acetate or styrene acrylates.
 16. An intumescent nanostructured material as set forth in claim 14, wherein the hard char includes one or a combination of sodium silicate or graphite.
 17. An intumescent nanostructured material as set forth in claim 10, wherein the intumescent material is combined with a blowing agent that thermally decomposes to produce gasses to facilitate formation of the foam.
 18. An intumescent nanostructured material as set forth in claim 10, wherein the intumescent material reacts to form the foam at temperatures at or above about 400° C.
 19. An intumescent nanostructured material as set forth in claim 10, wherein the non-woven member accounts for about 10% to about 50% of the dry weight of the intumescent nanostructured material and the intumescent material is in a range of from greater than 0% to about 70% of the dry weight of the intumescent nanostructured material.
 20. An intumescent nanostructured material as set forth in claim 10, further including a flame retardant for protecting the nanostructured materials from oxidation in the presence of the heat source.
 21. An intumescent nanostructured material as set forth in claim 20, wherein the ceramifying polymer material coating or impregnating the non-woven member accounts for about 25% of the dry weight of the intumescent nanostructured material and the flame retardant accounts for about 5% of the dry weight of the intumescent nanostructured material.
 22. An intumescent nanostructured material for thermal protection comprising: a yarn member coated or impregnated with a ceramifying polymer material comprising a silazane and defined by plurality of intermingled and twisted carbon nanotubes and graphene, wherein the carbon nanotubes having a diameter ranging from 1 to 30 nm and an aspect ratio of length to diameter greater than 100:1, and wherein the yarn member contains residual iron in an amount up to 15 wt % based on the total weight of the yarn member; and an intumescent material infiltrated into the yarn member, wherein the yarn member is configured to provide thermal conductivity along its length, and to provide scaffolding structure for promoting formation of a layer of thermally-insulating foam as the intumescent material reacts in the presence of heat, wherein the intumescent nanostructured material is coated with one or more of polyvinyl chloride, EPDM, and an aramid.
 23. An intumescent nanostructured material as set forth in claim 22, wherein the yarn member has a nanotube linear density of about 1 Tex to about 100 Tex.
 24. An intumescent nanostructured material as set forth in claim 22, wherein the nanotubes act as scaffolding for accommodating and holding the intumescent material in place.
 25. An intumescent nanostructured material as set forth in claim 22, wherein the nanotubes promote the foam to form with a substantially closed-cell structure.
 26. An intumescent nanostructured material as set forth in claim 22, wherein the intumescent material includes soft char, hard char, or a combination thereof.
 27. An intumescent nanostructured material as set forth in claim 26, wherein the soft char includes one or a combination of ammonium polyphosphate, pentaeyrthritol, and melamine in a binder of vinyl acetate or styrene acrylates.
 28. An intumescent nanostructured material as set forth in claim 26, wherein the hard char includes one or a combination of sodium silicate or graphite.
 29. An intumescent nanostructured material as set forth in claim 22, wherein the intumescent material is combined with a blowing agent that thermally decomposes to produce gasses to facilitate formation of the foam.
 30. An intumescent nanostructured material as set forth in claim 22, wherein the intumescent material reacts to form the foam at temperatures at or above about 400° C.
 31. An intumescent nanostructured material as set forth in claim 22, wherein the yarn member accounts for about 10% to about 80% of the dry weight of the intumescent nanostructured material and the intumescent material accounts for about 10% to about 90% of the dry weight of the intumescent nanostructured material.
 32. An intumescent nanostructured material as set forth in claim 22, further including a flame retardant for protecting the nanostructured materials from oxidation in the presence of the heat source.
 33. An intumescent nanostructured material as set forth in claim 32, wherein the ceramifying polymer material coating or impregnating the yarn member accounts for about 25% of the dry weight of the intumescent nanostructured material and the flame retardant accounts for about 5% of the dry weight of the intumescent nanostructured material.
 34. An intumescent nanostructured material for thermal protection comprising: a woven member coated or impregnated with a ceramifying polymer material comprising a silazane and defined by a plurality of nanostructured yarns of intermingled and twisted nanotubes and graphene, wherein the nanotubes have a diameter ranging from 1 to 30 nm and an aspect ratio of length to diameter greater than 100:1, the nanostructured yarns being woven, braided, or knitted with one another to form the woven member and wherein the woven member contains residual iron in an amount up to 15 wt % based on the total weight of the woven member; and an intumescent material infiltrated into the woven member, wherein the woven member is configured to provide in-plane thermal conductivity along pathways defined by the plurality of nanostructured yarns, wherein the intumescent nanostructured material is coated with one or more of polyvinyl chloride, EPDM, and an aramid.
 35. An intumescent nanostructured material as set forth in claim 34, wherein the nanotubes act as scaffolding for accommodating and holding the intumescent material in place.
 36. An intumescent nanostructured material as set forth in claim 34, wherein the nanotubes promote the foam to form with a substantially closed-cell structure.
 37. An intumescent nanostructured material as set forth in claim 34, wherein the intumescent material includes soft char, hard char, or a combination thereof.
 38. An intumescent nanostructured material as set forth in claim 37, wherein the soft char includes one or a combination of ammonium polyphosphate, pentaeyrthritol, and melamine in a binder of vinyl acetate or styrene acrylates.
 39. An intumescent nanostructured material as set forth in claim 37, wherein the hard char includes one or a combination of sodium silicate or graphite.
 40. An intumescent nanostructured material as set forth in claim 34, wherein the intumescent material is combined with a blowing agent that thermally decomposes to produce gasses to facilitate formation of the foam.
 41. An intumescent nanostructured material as set forth in claim 34, wherein the intumescent material reacts to form the foam at temperatures at or above about 400° C.
 42. An intumescent nanostructured material as set forth in claim 34, wherein the non-woven member accounts for about 10% to about 50% of the dry weight of the intumescent nanostructured material and the intumescent material accounts for about 0% to about 70% of the dry weight of intumescent nanostructured material.
 43. An intumescent nanostructured material as set forth in claim 34, further including a flame retardant for protecting the nanostructured materials from oxidation in the presence of the heat source.
 44. An intumescent nanostructured material as set forth in claim 43, wherein the ceramifying polymer material coating or impregnating the woven member accounts for about 25% of the dry weight of the intumescent nanostructured material and the flame retardant accounts for about 5% of the dry weight of intumescent nanostructured material.
 45. An intumescent nanostructured material for thermal protection, comprising: a member coated or impregnated with a ceramifying polymer material comprising a silazane and having a first plurality of nanostructured materials comprising nanotubes having a diameter ranging from 1 to 30 nm and an aspect ratio of length to diameter greater than 100:1 and graphene, wherein the member contains residual iron in an amount up to 15 wt % based on the total weight of the member; and a coating on a surface of the member, the coating including a second plurality of nanostructured materials comprising nanotubes having a diameter ranging from 1 to 30 nm and an aspect ratio of length to diameter greater than 100:1 and graphene and an intumescent material, wherein the intumescent material of the coating is configured to react in the presence of a heat source to form a foam for thermally insulating the member from the heat source, and wherein the plurality of nanostructured material of the coating is configured to support the intumescent material during formation of the foam, wherein the intumescent nanostructured material is coated with one or more of polyvinyl chloride, EPDM, and an aramid.
 46. An intumescent nanostructured material as set forth in claim 45, wherein the member is a non-woven sheet, a woven sheet, a yarn, or a network.
 47. An intumescent nanostructured material as set forth in claim 45, wherein the intumescent material includes soft char, hard char, or a combination thereof.
 48. An intumescent nanostructured material as set forth in claim 47, wherein the soft char includes one or a combination of ammonium polyphosphate, pentaeyrthritol, and melamine in a binder of vinyl acetate or styrene acrylates.
 49. An intumescent nanostructured material as set forth in claim 47, wherein the hard char includes one or a combination of sodium silicate or graphite.
 50. An intumescent nanostructured material as set forth in claim 45, wherein the intumescent material is combined with a blowing agent that thermally decomposes to produce gasses to facilitate formation of the foam.
 51. An intumescent nanostructured material as set forth in claim 45, wherein the intumescent material is coated onto, infiltrated into, or mixed with the member.
 52. An intumescent nanostructured material as set forth in claim 45, wherein the intumescent material reacts to form the foam at temperatures at or above about 400° C.
 53. An intumescent nanostructured material as set forth in claim 45, further including a flame retardant for protecting the nanostructured materials from oxidation in the presence of the heat source. 